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Pyridyldiamido transition metal complexes, production and use thereof
8710163 Pyridyldiamido transition metal complexes, production and use thereof
Patent Drawings:

Inventor: Hagadorn, et al.
Date Issued: April 29, 2014
Application:
Filed:
Inventors:
Assignee:
Primary Examiner: Lee; Rip A.
Assistant Examiner:
Attorney Or Agent: Bell; Catherine L.
U.S. Class: 526/172; 526/160; 526/161; 526/170; 526/351; 526/352; 556/51
Field Of Search: ;526/172; ;526/161; ;526/348; ;526/170; ;526/160; ;526/134; ;556/51
International Class: C08F 4/76; C08F 4/64; C08F 4/52; C07F 7/00
U.S Patent Documents:
Foreign Patent Documents: 2001-048925; 2001-48925; WO 2005/095469; WO 2007/067965; WO 2010/037059
Other References: Froese et al., Mechanism of Activation of a Hafnium Pyridyl-Amide Olefin Polymerization Catalyst: Ligand Modification by Monomer, J. Am. Chem.Soc., 2007, vol. 129, No. 25, pp. 7831-7840. cited by applicant.
Guerin et al., Synthesis, Structure, and Reactivity of Zirconium Alkyl Complexes Bearing Ancillary Pyridine Diamide Ligands, Organometallics, 1998, vol. 17, No. 23, pp. 5172-5177. cited by applicant.









Abstract: Pyridyldiamido transition metal complexes are disclosed for use in alkene polymerization.
Claim: What is claimed is:

1. A pyridyldiamido transition metal complex represented by the formula: (I) or (II): ##STR00011## wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; R.sup.1is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups; R.sup.11 is selected from the group consisting of substituted 5 or 6 membered aromatic rings; R.sup.10 is -E*(R.sup.12)(R.sup.13)--; E and E* are,independently, carbon, silicon, or germanium; each R.sup.12 and R.sup.13 is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R.sup.12 and R.sup.13may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R.sup.12 and R.sup.13 may be joined to form asaturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings; each R.sup.12* and R.sup.13* is independently selected from the group consisting of hydrogen, C1 to C5hydrocarbyls, and substituted C1 to C5 hydrocarbyls; R.sup.3, R.sup.4, and R.sup.5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacentR groups (R.sup.3 & R.sup.4 and/or R.sup.4 & R.sup.5) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additionalrings; R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.15, and R.sup.16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and whereinadjacent R groups (R.sup.6 & R.sup.7, and/or R.sup.7 & R.sup.15, and/or R.sup.16 & R.sup.15, and/or R.sup.8 & R.sup.9) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ringcarbon atoms and where substitutions on the ring can join to form additional rings; L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group; n is 0, 1, 2, 3, or4; L' is neutral Lewis base; w is 0, 1, 2, 3, or 4; Z is --(R.sup.14*).sub.pQ-J(R.sup.15*).sub.q-- where Q or J is bonded to R.sup.10; J is C or Si; Q is C, N, or Si; R.sup.14* and R.sup.15* are independently selected from the group consisting ofhydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R.sup.14* and R.sup.15* groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atomsand where substitutions on the ring can join to form additional rings; p is 1 or 2; and q is 1 or 2.

2. The complex of claim 1, wherein M is Ti, Zr, or Hf

3. The complex of claim 1, wherein R.sup.10 is represented by the formula: ##STR00012## where R.sup.12'' is hydrogen, alkyl, aryl, or halogen; and R.sup.13'' is hydrogen, alkyl, aryl, or halogen.

4. The complex of claim 1, wherein R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.15, and R.sup.16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl.

5. The complex of claim 1, wherein R.sup.1, R.sup.3, R.sup.4, and R.sup.5 each contain no more than 30 carbon atoms.

6. The complex of claim 4, wherein R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.15 each contain no more than 30 carbon atoms.

7. The complex of claim 1, wherein E and E* are carbon and R.sup.1 is selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, I, CF.sub.3, NO.sub.2, alkoxy,dialkylamino, hydrocarbyl, and substituted hydrocarbyls groups with from one to ten carbons.

8. The complex of claim 1, wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl; andeach L' is independently selected from the group consisting of ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines.

9. The complex of claim 1, wherein both R.sup.12 and R.sup.13 are a C.sub.1 to C.sub.100 alkyl group.

10. The complex of claim 1, wherein the complex is represented by formula (I).

11. The complex of claim 1, wherein the complex is represented by formula (II).

12. The complex of claim 1, wherein R.sup.12* and R.sup.13* are the same.

13. The complex of claim 1, wherein the complex is represented by formula (I) and R.sup.12* is H, R.sup.13* is a group containing from 1 to 5 carbons, M is a Group 4 metal, E is carbon and R.sup.10 is CH.sub.2.

14. The complex of claim 1, wherein the complex is represented by formula (II) and R.sup.12* is a group containing from 1 to 5 carbons, M is a Group 4 metal, E is carbon and R.sup.10 is CH.sub.2.

15. The complex of claim 1, wherein M is a Group 4 metal, E* is carbon and R.sup.10 is CH.sub.2.

16. The complex of claim 1, wherein R.sup.11 is selected from the group consisting of substituted 6 membered aromatic rings.

17. The complex of claim 1, wherein R.sup.11 is selected from the group consisting of substituted 5 or 6 membered rings where the ring atoms are carbon or heterocyclic rings having 1, 2 or 3 heteroatoms in the ring and where the substitution isa hydrocarbyl group, a heteroatom, or a heteroatom containing group.

18. The complex of claim 1, wherein R.sup.11 is a substituted aryl group.

19. The complex of claim 1, wherein R.sup.11 is a 2,6 or 2,4,6 substituted aryl group.

20. The complex of claim 1, wherein R.sup.11 is a 2,6 or 2,4,6 substituted aryl, where the substituents are methyl, ethyl, methoxy, propyl, tert-butyl, butyl, isopropyl, pentyl, hexyl, isobutyl, chloro, fluoro, bromo, iodo, trimethylsilyl, ortriethylsilyl.

21. The complex of claim 1, wherein R.sup.11 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisobutylphenyl, 2,5-dimethylphenyl, 2,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2,6-diisopropylphenyl, or2,4,6-triisopropylphenyl.

22. A process for preparing the pyridyldiamido complex of claim 2 comprising reaction of a pyridyldiamine with a group 4 transition metal complex of the general formula MY.sub.2L.sub.2L'.sub.W, where M is Ti, Zr, or Hf, Y is a deprotonatedamine or hydrocarbanion group; L is an anionic leaving group, where the L and Y groups may be the same or different and any two L and/or Y groups may be linked to form a dianionic group; L' is neutral Lewis base; and w is 0, 1, 2, 3, or 4.

23. A catalyst system comprising an activator and the complex of claim 1.

24. The catalyst system of claim 23, wherein the activator is an alumoxane.

25. The catalyst system of claim 23, wherein the activator is a non-coordinating anion.

26. A polymerization process comprising a) contacting one or more alkene monomers with a catalyst system comprising: i) an activator and ii) the pyridyldiamido transition metal complex of claim 1.

27. The process of claim 26, wherein the activator is an alumoxane.

28. The process of claim 26, wherein the activator is a non-coordinating anion.

29. The process of claim 26, wherein the monomer comprises ethylene.

30. The process of claim 26, wherein the monomer comprises propylene.

31. The process of claim 26, wherein the pyridyldiamido transition metal complex is supported.

32. The process of claim 26, wherein R.sub.6, R.sub.7, R.sub.8, and R.sub.9 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl.

33. The process of claim 26, wherein R.sup.11 is selected from the group consisting of substituted 5 or 6 membered rings where the ring atoms are carbon or heterocyclic rings having 1, 2 or 3 heteroatoms in the ring and where the substitutionis a hydrocarbyl group, a heteroatom, or a heteroatom containing group.

34. The process of claim 26, wherein R.sup.11 is a 6 membered ring.

35. The process of claim 26, wherein R.sup.11 is a 2,6 or 2,4,6 substituted aryl, where the substituents are methyl, ethyl, methoxy, propyl, tert-butyl, butyl, isopropyl, pentyl, hexyl, isobutyl, chloro, fluoro, bromo, iodo, trimethylsilyl, ortriethylsilyl.
Description:
 
 
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